WO2006077918A1 - Formule de caoutchouc ignifugé et produit en caoutchouc et matériau pour gaine de fil électrique obtenus à partir de ladite formule - Google Patents

Formule de caoutchouc ignifugé et produit en caoutchouc et matériau pour gaine de fil électrique obtenus à partir de ladite formule Download PDF

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WO2006077918A1
WO2006077918A1 PCT/JP2006/300727 JP2006300727W WO2006077918A1 WO 2006077918 A1 WO2006077918 A1 WO 2006077918A1 JP 2006300727 W JP2006300727 W JP 2006300727W WO 2006077918 A1 WO2006077918 A1 WO 2006077918A1
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component
rubber
flame retardant
mass
rubber composition
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PCT/JP2006/300727
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English (en)
Japanese (ja)
Inventor
Seiji Morioka
Mamoru Hasegawa
Kenji Hasegawa
Junji Koujina
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Jsr Corporation
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Priority to DE602006014250T priority Critical patent/DE602006014250D1/de
Priority to JP2006553947A priority patent/JPWO2006077918A1/ja
Priority to US11/814,416 priority patent/US20090099293A1/en
Priority to EP06711973A priority patent/EP1840163B1/fr
Publication of WO2006077918A1 publication Critical patent/WO2006077918A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/083—Copolymers of ethene with aliphatic polyenes, i.e. containing more than one unsaturated bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/28—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances natural or synthetic rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof

Definitions

  • the present invention relates to a flame retardant rubber composition capable of obtaining a vulcanized rubber capable of exhibiting excellent flame retardance in a high temperature atmosphere, and a rubber product and a wire coating material obtained therefrom. More specifically, the present invention relates to a flame retardant rubber composition capable of imparting sufficient mechanical strength (particularly tensile rupture strength) even by steam vulcanization, which is generally considered difficult to impart strength. is there.
  • Synthetic rubber has the same rubber elasticity as natural rubber, and also has many characteristics such as chemical resistance, oil resistance, and heat resistance compared to natural rubber. Used in a wide range of fields such as parts and civil engineering materials. In recent years, however, the use environment of parts (for example, rolls, belts, etc.) using synthetic rubber has become harsh as the performance of automobiles, electrical products, etc. increases. In particular, the ambient temperature used is steadily increasing, and there is a demand for a synthetic rubber that can exhibit excellent flame retardancy in a high temperature atmosphere.
  • halogen flame retardants exhibit excellent flame retardancy even in a small amount! ⁇ ⁇ Although it has an advantage, it generates corrosive and toxic gas when burned. There was still a challenge in terms of harmony. Therefore, methods for blending non-halogen flame retardants are being studied.
  • a resin composition containing a non-halogen flame retardant for example, a flame retardant polypropylene resin composition containing a polypropylene flame retardant and a phosphorus flame retardant such as ammonium polyphosphate is disclosed.
  • a flame retardant polypropylene resin composition containing a polypropylene flame retardant and a phosphorus flame retardant such as ammonium polyphosphate is disclosed.
  • a high-strength flame-retardant rubber composition in which a metal hydroxide-based flame retardant such as hydroxide-aluminum or hydroxide-magnesium is blended with styrene-a-olefin copolymer rubber.
  • Patent Document 2 for example, see Patent Document 2 .
  • the present applicant also has a flame retardant rubber composition in which a metal hydroxide flame retardant is combined with a rubber composition mainly comprising an unsaturated nitrile conjugated gen rubber and an ethylene OC-olefin-based random copolymer. Products have already been disclosed (see, for example, Patent Documents 3 and 4).
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2-263385
  • Patent Document 2 JP-A-6-107870
  • Patent Document 3 Japanese Patent Laid-Open No. 2003-160695
  • Patent Document 4 Japanese Patent Laid-Open No. 2004-262963
  • a resin composition or a rubber composition containing a phosphorus-based flame retardant as described in Patent Document 1 is corrosive and toxic when burned, as in the case of adding a halogen-based flame retardant. There is an advantage that no gas is generated. However, phosphorus is also an environmental pollutant, and the same problems as halogen-based flame retardants remain in terms of pollution prevention and environmental harmony. Another problem is that the phosphorus-based flame retardant has a hygroscopic property, and the occurrence of bleeding due to the hygroscopic property cannot be avoided. Although this bleed can be improved to some extent by blending a silane coupling agent, etc., the flexibility and flexibility of the rubber may be lowered by blending the silane coupling agent, etc., and the physical properties of the resulting rubber There was room for improvement.
  • a rubber composition containing a metal hydroxide flame retardant as described in Patent Document 2 is corrosive and toxic when burned, as in the case of adding a halogen flame retardant. Since it does not contain environmental pollutants such as phosphorus that does not generate gas, it has the advantage of being excellent in terms of pollution prevention and environmental harmony. However, a considerable amount of the metal hydroxide flame retardant needs to be blended in order to exhibit sufficient flame retardancy, and when such amount of metal hydroxide flame retardant is blended However, the flexibility and workability of the resulting rubber may be reduced, and the mechanical properties, particularly the tensile strength, may be reduced, and the physical properties of the resulting rubber are still not fully satisfactory.
  • the present invention has been made to solve the problems of the prior art as described above, and has excellent flame retardancy, and generally by steam vulcanization that is difficult to impart strength.
  • the present invention provides a flame retardant rubber composition capable of imparting sufficient mechanical strength (particularly tensile fracture strength).
  • the inventors have conceived that the above problems can be solved by adding a polyfunctional monomer to the rubber composition, and have completed the present invention.
  • the present invention provides the following flame retardant rubber composition, rubber product, and wire covering material.
  • Synthetic rubber (component A), flame retardant (component B), sulfur (component C) and polyfunctional monomer (component D) are essential components, A flame retardant rubber composition containing 10 to 200 parts by mass of B component, 0.1 to 15 parts by mass of C component, and 3 to 30 parts by mass of D component.
  • the component A includes at least one selected from the group power of ethylene'a-olefin-based copolymer rubber, unsaturated-tolyl'conjugated gen-based rubber, styrene.butadiene rubber and acrylic rubber.
  • the component A is ethylene'a-olefin-based copolymer rubber (component A-1) and Saturated-tolyl-conjugated gen-based rubber (A-2 component) as a constituent component, and the composition ratio of the A-1 component and the A-2 component is in the range of 5:95 to 85:15 [1] ⁇ Flame retardant rubber composition as described in [3]!
  • An electric wire covering material comprising a vulcanized rubber obtained by vulcanizing the flame retardant rubber composition according to any one of [1] to [8].
  • the flame-retardant rubber composition of the present invention has excellent flame retardancy and generally has mechanical strength that can be sufficiently satisfied even by steam vulcanization, which is generally difficult to impart strength (particularly tensile fracture). Strength).
  • the flame retardant rubber composition of the present invention comprises synthetic rubber (component A), flame retardant (component B), sulfur (component C).
  • component D a polyfunctional monomer (component D) as essential components, and these essential components are contained in a predetermined ratio.
  • the A component is selected from the group strength of ethylene'a-olefin-based copolymer rubber, unsaturated-tolyl'conjugated gen-based rubber, styrene'butadiene rubber and talyl rubber. It is preferable to use synthetic rubber containing at least one kind of rubber, exylene olefin copolymer rubber (A-1 component) and unsaturated-tolyl 'conjugated gen rubber (A-2 component). More preferably, it is a synthetic rubber.
  • A-1 component for example, ethylene 'propylene' non-conjugated gen terpolymer rubber (EPDM), ethylene 1-butene 'non-conjugated gen terpolymer rubber, 3 to 10 ethylene and carbon atoms.
  • EPDM ethylene 'propylene' non-conjugated gen terpolymer rubber
  • ethylene 1-butene 'non-conjugated gen terpolymer rubber 3 to 10 ethylene and carbon atoms.
  • random copolymers mainly composed of ⁇ -olefin and non-conjugated gen random copolymers mainly composed of ⁇ -olefin and non-conjugated gen.
  • Examples of " ⁇ -olefin having 3 to 10 carbon atoms” include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and the like. Of these, propylene and 1-butene are preferable.
  • non-conjugated gen examples include 1,4 pentagen, 1,4 monohexagen, 1,5 monohexagen, 1,7-octadiene, 1,9-decadiene, 3,6 dimethyl-1,7 -Octagen, 4,5 dimethyl-1,7-octagen, 5-methyl-1,8 nonagen, dicyclopentagen, 5 ethylidene-2 norbornene, 5 bur-2 norbornene, 2,5 norbornagen and the like. Of these, 1,4 hexagen, dicyclopentagen, and 5 ethylidene 2 norbornene are preferable.
  • a content of units derived from ethylene is less than 90 mole 0/0, be a Orefuin derived units are contained 10 mol 0/0 or more preferable. If the content of ethylene-derived units is 90 mol% or more and the content of a-olefin-derived units is less than 10 mol%, rubber flexibility may be inferior. It is not preferable.
  • units derived from ethylene and alpha - in the case where the total number of moles of Orefuin derived units is 100 mol 0/0 is usually 3-10 mol% equivalent amount, preferably 3 It is preferred to contain an equivalent amount of ⁇ 8 mol%.
  • the mu-one viscosity [ML (100 ° C)] of the ethylene / ⁇ -olefin-based copolymer is
  • the iodine value is usually 40 or less, preferably 5 to 30, and more preferably 7 to 20. If the iodine value exceeds 40, the cost increases and the rubber elasticity of the material may be lost, which is not preferable.
  • the crystallinity by X-ray diffraction measurement is usually 20% or less, preferably 15% or less. If the crystallinity exceeds 20%, the flexibility of the rubber tends to decrease, which is not preferable.
  • the polymerization method of the A-1 component is not particularly limited, but can be polymerized in the presence of a conventionally known catalyst such as a vanadium catalyst, a titanium catalyst, or a metalocene catalyst. More specifically, in the case of a vanadium-based catalyst, ethylene, a one-year-old refin, and use in the presence of a catalyst comprising a vanadium compound soluble in at least one solvent and at least one organoaluminum compound. In this case, a method of polymerizing non-conjugated gen may be mentioned. At this time, polymerization may be carried out while supplying hydrogen as a molecular weight regulator as required. Polymerization can also be carried out by gas phase method (fluidized bed or stirred bed) or liquid phase method (slurry method or solution method) or any other method.
  • a conventionally known catalyst such as a vanadium catalyst, a titanium catalyst, or a metalocene catalyst. More specifically, in the case of a vanadium-based catalyst
  • a reaction product of at least one selected with an alcohol examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, t-butanol, n-hexanol, n-octanol, 2-ethylhexanol, n -Decanol, n-dodecanol and the like.
  • Examples of the “organoaluminum compound” include triethylaluminum, triisobutylaluminum, tri- n -hexylaluminum, jetylaluminum monochloride, disobutylaluminum monochloride, ethylaluminum sesquichloride, butyl Aluminum- Examples thereof include lumsesquic chloride, ethyl aluminum dichloride, butyl aluminum dichloride, and methylaluminoxane which is a reaction product of trimethylaluminum and water.
  • ethyl aluminum sesquichloride butyl aluminum sesquichloride, a mixture of ethyl aluminum sesquichloride and triisobutyl aluminum, a mixture of triisobutyl aluminum and butyl aluminum sesquichloride, .
  • a hydrocarbon solvent is used, among which n-pentane, n-hexane, n-heptane, n-year-old kutan, iso-year-old kutan, It is preferable to use cyclohexane or the like.
  • hydrocarbon solvents can be used alone or in admixture of two or more.
  • Ethylene A Orefuin copolymer rubber of the present invention may be a softening agent to be described later is previously added at the time of polymerization oil-extended polymers.
  • copolymer rubber of unsaturated-tolyl and conjugated diene copolymer of unsaturated-tolyl and copolymerizable monomer containing polar group other than conjugated digen and unsaturated-tolyl
  • rubber for example, rubber.
  • Examples of "unsaturated-tolyl” include acrylonitrile, methacrylic mouth-tolyl, a -ethyl acrylonitrile, a -isopropyl acrylonitrile, a -black mouth acrylonitrile, a -fluoroacrylonitrile, etaly mouth-tolyl and the like. Can be mentioned. Of these, acrylonitrile is preferred.
  • conjugated gen examples include butadiene, isoprene, 1,3 hexagen, 2,3-dimethylbutadiene, 2 trimethoxysilyl 1,3 butadiene, 1,3 pentagene, 2,4 dimethyl-1, 3 Butadiene can be mentioned. Of these, butadiene and isoprene are preferred. These conjugate gens may be used singly or in combination of two or more.
  • Examples of the "unsaturated-copolymerizable monomer containing a polar group other than tolyl” include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and n-butyl acrylate. , T-butyl acrylate, s-butyl acrylate, 2-methylbutyl acrylate, 3-methylbutyl acrylate, n-hexyl acrylate, n-heptyl acrylate , N-octyl acrylate, 2-ethylhexyl acrylate,
  • acrylic acid ethyl acrylate, ⁇ -butyl acrylate, t-butyl acrylate, and s-butyl acrylate are preferable.
  • These copolymerizable monomers may be used alone or in combination of two or more.
  • the content of conjugated gen-derived units is usually 15 to 65% by mass, preferably 20 to 50% by mass. Less than 15% by mass Then, rubber elasticity tends to decrease, which is not preferable. On the other hand, if it exceeds 65 mass 0/0, the compatibility with Mizusani ⁇ magnesium when using Mizusani ⁇ magnesium as a flame retardant agent Akui ⁇ Shi, mechanical strength of the resulting rubber composition It tends to decrease, which is preferable.
  • the content of unsaturated-tolyl-derived units is preferably 33 to 70% by mass, more preferably 40 to 60% by mass. If it is less than 33% by mass, V-magnesium hydroxide is used as a flame retardant, and the compatibility with magnesium-hydroxide will deteriorate, resulting in a decrease in mechanical strength of the resulting rubber composition. This is not preferable. On the other hand, if it exceeds 70% by mass, the rubber elasticity may decrease, which is preferable.
  • the content is usually 0 to 60% by mass, preferably 0 to 50% by mass. is there. If it exceeds 60% by mass, the rubber elasticity tends to decrease, such being undesirable.
  • the polymerization method of the A-2 component is not particularly limited, and examples thereof include a radical polymerization method and an anion polymerization method.
  • examples of the radical polymerization method include a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method, and an emulsion polymerization method that provides a stable emulsion dispersion at the end of the polymerization is particularly preferable.
  • a method of this emulsion polymerization a monomer mixed in a predetermined ratio is emulsified in an aqueous medium in the presence of an emulsifier, and polymerization is initiated by a radical polymerization initiator to reach a predetermined polymerization conversion rate. Thereafter, a method of stopping the polymerization with a polymerization stopper may be mentioned.
  • Examples of the emulsifier include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant.
  • An anionic surfactant for example, a carbon number of 10 or more is used.
  • Long chain fatty acid salts, rosinates and the like are widely used. More specifically, strong potassium acid, lauric acid, myristic acid, palmitic acid, oleic acid, potassium salt of stearic acid or sodium salt can be preferably used.
  • These emulsifiers can be used alone or in a mixture of two or more.
  • Radar polymerization initiators include benzoyl peroxide, lauroyl peroxide, tert-butyl hydroperoxide, tamen hydroperoxide, paramentane hydride oral peroxide, di-tert-butyl peroxide and dicumyl Organic peroxides such as peroxides can be used. It is also represented by azobisisopetit mouth-tolyl. Diazo compounds; inorganic peroxides typified by potassium persulfate; and redox catalysts typified by combinations of these peroxides and ferrous sulfate can also be used. These radical polymerization initiators may be used alone or in a combination of two or more.
  • a chain transfer agent may be used to adjust the molecular weight of the two components.
  • alkyl mercaptans such as tert-dodecyl mercaptan and n-dodecyl mercaptan; carbon tetrachloride, thioglycols, diterpene, terpinolene, and ⁇ -terpinenes can be used.
  • each monomer, emulsifier, radical polymerization initiator, chain transfer agent, etc. may be charged all at once into the reaction vessel to initiate the polymerization. It may be added continuously or intermittently when the reaction is continued.
  • This polymerization is preferably carried out at a temperature of usually 0 to 100 ° C., preferably 0 to 80 ° C. in an atmosphere from which oxygen is removed. During the reaction, the reaction conditions such as temperature and stirring can be appropriately changed.
  • the polymerization method may be a continuous method or a batch method.
  • the polymerization is generally stopped by adding a polymerization terminator when a predetermined polymerization conversion rate is reached.
  • a polymerization terminator for example, amine compounds such as hydroxylamine and jet hydroxylamine; quinone compounds such as hydroquinone;
  • the A-2 component can be obtained by removing the unreacted monomer from the reaction system by a method such as steam distillation and coagulating the latex as necessary.
  • 0 ° C) is preferably 20 to 200. If it is less than 20, it is not preferable because the mechanical strength is lowered. On the other hand, if it exceeds 200, processing characteristics such as kneading are deteriorated.
  • component A is composed of ethylene 'a-olefin copolymer rubber (A-1 component) and unsaturated-tolyl' conjugated gen rubber (A-2 component), A — It is preferable that the composition ratio of component 1 to component A-2 is in the range of 5:95 to 85:15.
  • the total mass of the A-1 component and the A-2 component is 100 parts by mass, if the A-1 component is less than 5 parts by mass, the weather resistance tends to deteriorate. On the other hand, if it exceeds 85 parts by mass, flame resistance and oil resistance In some cases, it is inferior.
  • “Flame retardants” include, for example, antimony flame retardants such as antimony trioxide and antimony pentoxide; zinc flame retardants such as zinc borate, zinc sulfate, and zinc stannate; triphenyl phosphate, cresyl diphenol Phosphorus flame retardants such as phosphate, phenol resorcinol polyphosphate, bisphenol I A-bis (diphenyl phosphate), bisphenol A A-bis (dichlorophosphate); hydroxide ⁇ aluminum, hydroxide ⁇ Metal hydroxide and flame retardants such as magnesium are known. However, in the present invention, it is preferable to use a metal hydroxide flame retardant, particularly magnesium hydroxide.
  • the metal hydroxide flame retardant those having good crystal growth and less agglomeration are preferable.
  • the BET specific surface area is 20 m 2 Zg or less, preferably 3 to: L0m 2 Zg, and the average secondary particle size is SO. 2 to 5 ⁇ m, preferably ⁇ or 0.5.
  • the metal hydroxide may be either a synthetic product or a natural product as long as it satisfies the above characteristics.
  • a synthetic product of magnesium hydroxide is contacted in an aqueous medium under conditions that allow sufficient contact between magnesium salt (or magnesium nitrate) and ammonia (or potassium hydroxide), and then under pressure. It is obtained by heating with.
  • natural products are preferable in terms of cost because they are cheaper than synthetic products.
  • the surface of the metal hydroxide has a fatty acid such as stearic acid, oleic acid, palmitic acid, lauric acid, arachidic acid, or an alkali metal salt thereof; paraffin, wax, polyethylene wax, or a modified product thereof; organic Organic metal compounds such as borane and organic titanates; those treated with a silane coupling agent or the like can be used.
  • a fatty acid such as stearic acid, oleic acid, palmitic acid, lauric acid, arachidic acid, or an alkali metal salt thereof
  • paraffin, wax, polyethylene wax, or a modified product thereof organic Organic metal compounds such as borane and organic titanates
  • those treated with a silane coupling agent or the like can be used.
  • the metal hydroxide that has been surface-treated with a silane coupling agent in advance, or the combination of a metal hydroxide and a silane coupling agent has a remarkable effect of improving the tensile strength of rubber. It is preferable
  • the amount of the silane coupling agent to be added to the metal hydroxide in the case of treating with the silane coupling agent is usually 0.1 to 3 parts by mass, preferably 100 parts by mass of the metal hydroxide. 0.3 to 1 part by mass. 0. If it is less than 1 part by mass, the cohesive strength of the metal hydroxide is strong. Since the dispersibility to a rubber composition tends to be inferior, it is not preferable. On the other hand, if the amount exceeds 3 parts by mass, the dispersibility will not be further improved, which is not preferable in terms of cost.
  • a method of surface-treating the metal hydroxide with a silane coupling agent a conventionally known dry method or wet slurry method can be employed.
  • a metal hydroxide and a silane coupling agent may be added to the rubber composition, and surface treatment may be performed while mixing.
  • Silane coupling agents include, for example, butyltrimethoxysilane, vinyltriethoxysilane, butyltris (j8-methoxyethoxy) silane, butyltrichlorosilane, butyltrimethoxysilane, N- (j8-aminoethyl) ⁇ -amino Propyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ - aminopropyltriethoxysilane, ⁇ -glycid
  • the metal hydroxide is surface-treated with a higher fatty acid or an alkali metal salt thereof, a higher fatty acid (or an alkali metal salt thereof) dissolved in the metal hydroxide at a high temperature or with a solvent. It can be sprayed and surface treated by a dry method using a Henschel mixer or the like. Further, it is also possible to add a metal hydroxide and a higher fatty acid (or an alkali metal salt thereof) to the rubber composition and perform surface treatment while mixing.
  • the addition amount of the higher fatty acid or the alkali metal salt thereof to the metal hydroxide may be an amount that can cover 10 to 80%, preferably 15 to 50%, of the specific surface area by the BET method.
  • the content of the B component is 10 to 200 parts by mass, preferably 30 to 150 parts by mass with respect to 100 parts by mass of the A component. If it is less than 10 parts by mass, there is a possibility that sufficient flame retardancy may not be obtained. On the other hand, when the amount exceeds 200 parts by mass, the mechanical strength is remarkably lowered.
  • Sulfur mainly acts as a crosslinking agent for the A component.
  • sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur and the like.
  • Content of C component is 0.1-15 mass parts with respect to 100 mass parts of A component, Preferably it is 0.1-: LO mass part, More preferably, it is 0.5-5 mass parts. If the amount is less than 1 part by mass, the crosslinking reaction may not proceed, which is not preferable. On the other hand, when the amount exceeds 15 parts by mass, the crosslinking reaction is excessive, and there is a risk of losing rubber properties.
  • a sulfur-containing compound that releases active sulfur at the crosslinking temperature may be used in combination with sulfur.
  • sulfur-containing compounds include sulfur chloride, sulfur dichloride, polymer polysulfide, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, dimethyl
  • sulfur-containing compounds include sulfur chloride, sulfur dichloride, polymer polysulfide, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, dimethyl
  • sulfur-containing compounds include sulfur chloride, sulfur dichloride, polymer polysulfide, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, dimethyl
  • selenium dithiocarbamate include sulfur chloride, sulfur dichloride, polymer polysulfide, morpholine disulfide
  • polyfunctional monomer means a monomer having two or more polymerizable functional groups in one molecule.
  • a polyfunctional acrylate compound or a polyfunctional isocyanate compound can be suitably used.
  • These polyfunctional monomers may be used alone or in combination of two or more.
  • the component D is preferably a polyfunctional monomer that is liquid at room temperature (25 ° C).
  • a polyfunctional monomer that is liquid at room temperature is preferred in that it has the effect of reducing the viscosity of the rubber composition.
  • Examples of such a multifunctional monomer include trimethylpropane trimethacrylate (for example, trade name: Hi-Cros M, manufactured by Seei Seigaku Co., Ltd.).
  • the content of component D is 3 to 30 parts by mass, preferably 4 to 25 parts by mass, and particularly preferably 5 to 20 parts by mass with respect to 100 parts by mass of component A. If the amount is less than 3 parts by mass, the effect of improving the physical properties is poor and satisfactory mechanical strength may not be obtained. On the other hand, if it exceeds 30 parts by mass, the flame retardancy may decrease, which is not preferable. [0070] These polyfunctional monomers are sometimes used as a crosslinking agent when a peroxide is used as a crosslinking agent.
  • the amount used thereof is the amount used when a peroxide is used as a crosslinking agent (usually 100 mass of synthetic rubber). (About 0.1-2 parts by weight with respect to parts)) By increasing the amount significantly (about 3-30 parts by weight with respect to 100 parts by weight of synthetic rubber), the mechanical strength of the resulting rubber is improved. It is characterized by the fact that it was found.
  • the flame retardant rubber composition of the present invention preferably contains silica (E component) as a constituent component in addition to the essential components.
  • Silica is preferable in that it acts as a reinforcing agent and a filler and has an effect of improving mechanical strength, particularly tensile strength at break, in combination with the D component.
  • silica for example, silica such as wet silica and dry silica can be suitably used.
  • component E is 2 to: LOO parts by mass, preferably 10 to 100 parts by mass of component A
  • a conventionally known filler may be used in combination with silica.
  • Conventionally known fillers include, for example, heavy calcium carbonate, pepper, light calcium carbonate, ultrafine activated calcium carbonate, special calcium carbonate, basic magnesium carbonate, kaolin clay, calcined clay, neuroflight clay, silane Treated clay, synthetic calcium silicate, synthetic magnesium silicate, synthetic aluminum silicate, magnesium carbonate, hydroxyaluminum hydroxide, magnesium hydroxide, magnesium oxide, kaolin, sericite, talc, fine talc, wollastonite, zeolite, Zonotonite, Asbestos, PMF (Processed Mineral Fiber), Sepiolite, Potassium titanate, Elastadite, Gypsum fiber, Glass balun, Silica balun, Hyde mouth talcite, Fly ash balun, Shirasu balun, Carbon balun, Alumina, Sulfur Barium, aluminum sulfate, calcium sulfate, molybdenum disulfide, and the
  • additives other than the above-described constituents for example, a crosslinking accelerator, a crosslinking assistant, a plasticizer, and the like are blended.
  • carbon black reinforcing agents, metal oxides, softeners, antiaging agents, processing aids, and the like can be blended in appropriate amounts.
  • N-cyclohexyloxy-2-benzothiazolylsulfenamide N-oxydiethylene-2-benzothiazolylsulfenamide, N, N-diisopropyl-1-benzothiazoli Sulfenamide compounds such as sulfenamide; 2 mercaptobenzothiazole, 2- (2,4, -di-trifluoro) mercapto benzothiazole, 2- (4,1 morpholinodithio) benzothiazole, dibenzothiazyl disulfide, etc.
  • guanidine compounds such as diphenylguanidine, diisotolylguanidine, diortho-tolylguanidine, ortho-tolylbiguanide, diphenyldazine phthalate, etc .;
  • Imidazoline compounds thiocarbalide, jetylthiourea, dibutylthiourea, trimethylthiourea, diosotrilthiourea and other thiourea compounds; tetramethylthiuram monosulfide, tetramethylthiuramdisulfide, tetraethylthiuramdisulfide , Tetrabutyl thiuram disulfide, pentamethylene thiuram tetrasulfide, and other thiuram compounds; zinc dimethyldithiocarbamate, zinc decyldithiocarbamate, zinc n-butyldithiocarbamate, ethyl ether Dithioate compounds such as zinc dithiocarbamate, zinc butylphenol dithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, tellurium dimethyldithiocarbamate; xanthat
  • Plasticizers include dimethyl phthalate, jetyl phthalate, dibutyl phthalate, diisobutino phthalate, dioctino phthalate, butino leoctino phthalate, di (2-ethylhexyl) phthalate, diiso Phthalate esters such as octyl phthalate and diisodecyl phthalate; dimethyl adipate, diisobutyl adipate, di (2-ethylhexyl) Adipate, diisooctyl adipate, diisodecyl adipate, octyldecyl adipate, di (2-ethylhexyl) azelate, diisooctylazelate, diisobutylazelate, dibutyl sebacate, di (2-ethylhexyl) sebacate Fatty acid esters such as di-oct
  • Trimellitic acid esters such as trimellitic acid isodecyl ester, trimellitic acid octyl ester, trimellitic acid n-octyl ester, trimellitic acid-based isol ester; Xyl) fumarate, diethylene glycol monooleate, glyceryl monoricinoleate, trilauryl phosphate, tristearyl phosphate, tri (2-ethylhexyl) phosphate, epoxidized soybean oil, polyether ester and the like.
  • These plasticizers may be used alone or in a combination of two or more. Further, the plasticizer may be used by dispersing in advance in unsaturated-tolyl-conjugated gen-based rubber.
  • Examples of carbon black reinforcing agents include SAF carbon black, ISAF carbon black, HAF carbon black, FEF carbon black, GPF carbon black, SRF carbon black, FT carbon black, MT carbon black, acetylene carbon black, and gasket. Examples include chain black. These reinforcing agents may be used alone or in a combination of two or more.
  • Examples of the metal oxide include zinc white, activated zinc white, surface-treated zinc white, zinc carbonate, composite zinc white, composite active zinc white, surface-treated magnesium oxide, magnesium oxide, calcium hydroxide, electrode Examples include fine calcium hydroxide, lead monoxide, red lead, white lead, and the like. These metal oxides may be used individually by 1 type, and 2 or more types may be mixed and used for them.
  • Examples of the softener include petroleum softeners, vegetable oil softeners, and subs. Aromatic, naphthenic, paraffinic softeners, etc. as oil softeners, and castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, radish oil, peanut oil, Examples of subs such as brazing wax include black sub, white sub, and straw sub.
  • Examples of the antiaging agent include naphthylamine, diphenylamine, p-phenol. Diamine, quinoline, hydroquinone derivative, (mono, bis, tris, poly) phenol, thiobisphenol, hindered phenol, phosphite, imidazole, dithiocarbamate nickel salt, phosphorus Examples thereof include acid-based anti-aging agents. These anti-aging agents may be used alone or in combination of two or more.
  • processing aid examples include stearic acid, oleic acid, lauric acid, zinc stearate, calcium stearate, potassium stearate, sodium stearate, stearylamine and the like. These anti-aging agents may be used alone or in combination of two or more.
  • the flame retardant rubber composition of the present invention may contain a rubber component other than the A component.
  • rubber components include styrene butadiene copolymer rubber, butadiene rubber, isoprene rubber, butadiene isoprene copolymer rubber, butadiene styrene-isoprene copolymer rubber, acrylic rubber, butyl rubber, natural rubber, chloroprene rubber, and the like. Can be used.
  • the flame retardant rubber composition of the present invention can be made into a rubber product by the following method, for example.
  • a kneading machine such as a Banbury mixer 70- Kneading at a temperature of 180 ° C.
  • sulfur, a crosslinking accelerator and the like are further blended using a Banbury mixer, a mixing roll or the like, and formed into a predetermined shape.
  • crosslinking is performed by steam vulcanization or press vulcanization at a temperature of 130 to 200 ° C. to obtain a rubber product having vulcanized rubber strength.
  • the flame retardant rubber composition of the present invention has a tensile breaking strength of vulcanized rubber obtained by steam vulcanization of 13 MPa or more, which is comparable to chlorobrene rubber conventionally used as a wire coating material. Has tensile strength at break. Therefore, it can be suitably used as an alternative material for chloroprene rubber, and contributes to dehalogenation of the wire coating material.
  • Example [0087] Hereinafter, the flame-retardant rubber composition of the present invention will be described more specifically with reference to Examples. However, since these examples show only some embodiments of the present invention, the present invention should not be construed as being limited to these examples.
  • the measurement conditions were ML (125 ° C).
  • durometer A hardness was measured according to JIS K6253 and evaluated according to the following criteria.
  • ⁇ Oxygen index 26 or higher (good), X: Oxygen index less than 26 (poor).
  • acrylonitrile' butane acrylonitrile' butane
  • B component Manufactured by Kogyo Co., Ltd. [volume average particle diameter 2.5 m, specific surface area 8.9 cmVg]) 55 parts by mass
  • D component trimethylpropane trimetatalylate (trade name: Hicross M, Seiko Chemical Co., Ltd.) 10 parts by mass
  • E component 20 parts by mass of wet silica (trade name: Toxeal GU, manufactured by Soda Tokuyama)
  • MAF carbon black (trade name: Seast Gl 16HM, manufactured by Tokai Carbon Co., Ltd.) 15 parts by mass, as a metal oxide, activated zinc white (trade name: active zinc white azo, positive 5 parts by weight, stearic acid (trade name: LUNAC S-30, manufactured by Kao Corporation), 1 part by weight, ⁇ -methacryloxyprovirtrimethoxysilane (product) Name: TSL8370, manufactured by GE Toshiba Silicone) Using 1 part by mass, knead them for 5 minutes at 100 to 150 ° C using a Banbury mixer (model: 1. 7BB2 type, manufactured by Kobe Steel). A formulation was prepared.
  • the flame retardant rubber composition described above was extruded into a flat plate shape using an extruder ( ⁇ 50 mm), and directly vulcanized at 150 ° C for 45 minutes using a vulcanizing can to obtain a vulcanized rubber. . Thereafter, a molded product whose thickness was increased by vulcanization shrinkage or the like was polished with a grinder so as to have a thickness of about 2 mm, thereby producing a sheet-like evaluation sample. This evaluation sample was subjected to physical property measurement. The results are shown in Table 1.
  • the flame retardant rubber composition described above is applied to a sheet mold (15 cm X 15 cm X O. 2 cm) and a pre-mold. Using a plastic molding machine, press vulcanization was performed by heating at 170 ° C for 20 minutes to obtain vulcanized rubber, and a 2 mm thick sheet-like evaluation sample was produced. This evaluation sample was subjected to physical property measurement. The results are shown in Table 1.
  • the flame retardant rubber compositions of Examples 1 to 6 were excellent in mechanical properties, particularly tensile strength at break. Specifically, it was possible to provide a tensile fracture strength (13 MPa or more) that can be sufficiently satisfied even by steam vulcanization, which is generally considered to be difficult to impart strength. Among them, the vulcanized rubbers obtained from the flame retardant rubber compositions of Examples 1, 2, and 6 showed a tensile breaking strength exceeding 15 MPa even by steam vulcanization, and showed very good results.
  • the flame-retardant rubber composition of the present invention has excellent flame retardancy, it has rolls, belts, sealing materials, insulating tapes for copying machines, printers, and the like, as well as flame resistance and oil resistance. It can be used in many applications such as hoses required and seals in the building materials field. And since the flame-retardant rubber composition of the present invention is excellent in mechanical properties, in particular, tensile strength at break, it can be particularly suitably used as a wire covering material for in-device wiring and automobile harnesses.

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Abstract

La présente invention décrit une formule de caoutchouc ignifugé comprenant un caoutchouc synthétique (composant A), un agent ignifugeant (composant B), du soufre (composant C) et un monomère polyfonctionnel (composant D) au titre de composants essentiels, sachant que pour 100 parts en masse de composant A, il est inclus entre 10 et 200 parts en masse de composant B, entre 0,1 et 15 parts en masse de composant C, et entre 3 et 30 parts en masse de composant D. La présente invention décrit ainsi une formule de caoutchouc ignifugé dont les capacités ignifugeantes sont excellentes et dans les propriétés mécaniques (en particulier la résistance à la rupture en tension) sont très satisfaisantes, en dépit du fait qu'il soit généralement considéré comme difficile de conférer de la résistance à un matériau par vulcanisation à la vapeur.
PCT/JP2006/300727 2005-01-21 2006-01-19 Formule de caoutchouc ignifugé et produit en caoutchouc et matériau pour gaine de fil électrique obtenus à partir de ladite formule WO2006077918A1 (fr)

Priority Applications (4)

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DE602006014250T DE602006014250D1 (de) 2005-01-21 2006-01-19 Flammhemmende kautschukzusammensetzung und kautschukprodukt daraus sowie beschichtungsmaterial für einen elektrischen draht
JP2006553947A JPWO2006077918A1 (ja) 2005-01-21 2006-01-19 難燃性ゴム組成物、並びにそれから得られるゴム製品及び電線被覆材
US11/814,416 US20090099293A1 (en) 2005-01-21 2006-01-19 Flame retardant rubber composition and obtained therefrom, rubber product and electric wire coating material
EP06711973A EP1840163B1 (fr) 2005-01-21 2006-01-19 Composition de caoutchouc ignifuge, produit en caoutchouc et matériau de revêtement pour fil électrique obtenus à partir de ladite composition

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JP2009269939A (ja) * 2008-04-30 2009-11-19 Hitachi Cable Ltd ノンハロゲン難燃樹脂組成物及びこれを用いた電線・ケーブル
CN104311922A (zh) * 2014-10-30 2015-01-28 安徽电信器材贸易工业有限责任公司 一种无卤环保电缆料及其制备方法
JP2021084923A (ja) * 2019-11-25 2021-06-03 北川工業株式会社 アクリルゴム系組成物及び振動減衰材

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US8490666B2 (en) * 2008-12-08 2013-07-23 Philippe Gerard Germain Margot Fire resistant tire
JP5650033B2 (ja) * 2011-03-29 2015-01-07 富士フイルム株式会社 難燃性樹脂組成物、その製造方法、及び成形品
CN103483805B (zh) * 2013-09-08 2015-09-16 安徽万博电缆材料有限公司 一种环保电缆绝缘层材料的配方
US10680256B2 (en) * 2016-03-31 2020-06-09 Sumitomo Riko Company Limited Sealing member for a fuel cell
DE102016215342A1 (de) 2016-08-17 2018-02-22 Contitech Elastomer-Beschichtungen Gmbh Kautschukmischung und elastomerer Artikel mit flammhemmenden Eigenschaften
DE102016215333A1 (de) 2016-08-17 2018-02-22 Contitech Luftfedersysteme Gmbh Artikel, insbesondere ein Luftfederbalg, ein Metall-Gummi-Element oder ein Schwingungsdämpfer
CN109320788A (zh) * 2017-07-31 2019-02-12 傲优新材料科技（上海）有限公司 一种阻燃橡胶地板及其制备方法
JP7306844B2 (ja) * 2019-03-26 2023-07-11 株式会社バルカー シール材用ゴム組成物およびこれを用いたシール材
CN111171463B (zh) * 2020-02-14 2022-09-06 长欣胶业(上海)有限公司 一种降低水中三氯甲烷增加量的混炼胶及其制备方法
CN115368631A (zh) * 2022-09-22 2022-11-22 镇江朗赛夫新材料科技有限公司 一种组合物、阻燃橡胶和制备方法、及胶管

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JP2008257925A (ja) * 2007-04-02 2008-10-23 Furukawa Electric Co Ltd:The 絶縁電線
JP2009269939A (ja) * 2008-04-30 2009-11-19 Hitachi Cable Ltd ノンハロゲン難燃樹脂組成物及びこれを用いた電線・ケーブル
CN104311922A (zh) * 2014-10-30 2015-01-28 安徽电信器材贸易工业有限责任公司 一种无卤环保电缆料及其制备方法
JP2021084923A (ja) * 2019-11-25 2021-06-03 北川工業株式会社 アクリルゴム系組成物及び振動減衰材
JP7323928B2 (ja) 2019-11-25 2023-08-09 北川工業株式会社 アクリルゴム系組成物及び振動減衰材

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CN101146857A (zh) 2008-03-19
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